Sulfoxide hemithioindigo tweezers – visible light addressable capture and release

Bartelmann, Thomas; Gnannt, Frederik; Zitzmann, Max; Mayer, Péter; Dube, Henry

doi:10.1039/d0sc04981f

Cited by 20 publications

(17 citation statements)

References 73 publications

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“…Molecular tweezers, which were introduced by Whitlock, possess open-ended, cleft-shaped cavities characterized by two flat aromatic pincers connected with specific tethers. Various guest molecules are accommodated within the cleft-shaped cavities via supramolecular interactions, such as metal–ligand coordination, π–π stacking interactions, donor–acceptor interactions, and hydrogen bonding interactions. − Various molecular tweezers with various pincer units have been developed and show unique guest selections that are determined by the structural and electronic nature of cleft-shaped cavities. Molecular tweezers offer various applications to develop sensory systems, supramolecular polymers, molecular machines, and so on. − …”

Section: Introductionmentioning

confidence: 99%

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Hisano

Haino

2022

J. Org. Chem.

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The host–guest complexation of a bisporphyrin cleft with various electron-deficient guest molecules was studied in solution and in the solid-state. X-ray crystal structures of a bisporphyrin cleft with naphthalene dianhydride and 2,4,7-trinitrofluorenone reveal that these guest molecules were located within the bisporphyrin cleft and formed ideal π–π stacking interactions in a host–guest ratio of 1:1. Isothermal titration calorimetry determined the binding constants and thermodynamic parameters for the 1:1 host–guest complexations in 1,2-dichloroethane and toluene. Two types of enthalpy–entropy compensation effects were found: (1) The tightly stacked host–guest structures restrict guest movement within the cleft, which results in significant desolvation with large intrinsic entropies. (2) The loosely bound guests maintain their molecular freedom within the bisporphyrin cleft, which leads to less desolvation with small intrinsic entropies. Chiral guest encapsulation directed the clockwise and anticlockwise twisted conformations of the bisporphyrin units, which induced bisignate CDs.

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Section: Introductionmentioning

confidence: 99%

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Hisano

Haino

2022

J. Org. Chem.

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“…In a subsequent study, 21 was oxidized to obtain its sulfoxide derivative, which had improved photoswitching properties, thermal stability, as well as binding affinity. 76 Although the overall absorption was blue-shifted relative to the parent compound, now 83% of the E isomer could be produced using 405 nm light and 80% of the Z isomer was recovered by irradiation with 470 nm light. Again, the E form did practically not bind electron-deficient aromatic guest, but the Z form did with an elevated binding constant of K a = 4.1 × 10 3 M −1 in chloroform at −20 °C ( vs. K a = 2.3 × 10 3 M −1 for Z -21).…”

Section: Hemi-thioindigomentioning

confidence: 99%

Photoswitchable molecular tweezers: isomerization to control substrate binding, and what aboutvice versa?

Wezenberg

2022

Chem. Commun.

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“…For instance, Zimmerman et al took a step further from the flexible Whitlock tweezer and synthesized a conformationally more restricted system to prevent mono intercalation into DNA (Figure a). , The newly designed tweezer equipped with an additional H-bonding site proved to be an efficient receptor for some important analytes, such as adenine . Further developments in the field by Klärner , (Figure a) and others − resulted in the creation of semirigid systems possessing a small yet tangible degree of conformational freedom. In this line of research, the work of Harmata et al is worthy of a special mention as they synthesized one of the first chiral molecular tweezers based on Kagan ether.…”

Section: Introductionmentioning

confidence: 99%

Fully Supramolecular Chiral Hydrogen-Bonded Molecular Tweezer

et al. 2022

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Molecular tweezers are open-ended, cavity-possessing U-shaped molecular architectures with high potential for various applications in supramolecular chemistry. Their covalent synthesis, however, is often tedious and the structures obtained lack structural responsiveness beyond the limited conformational flexibility of the scaffold. Herein we present a proof-of-concept study on the design, synthesis, assembly, and transformations of a novel supramolecular constructa fully noncovalent molecular tweezer. The supramolecular tweezer was assembled from a set of four building blocks, composed of two identical molecular angle bars and two flat aromatic extension wings, using hydrogen bonding only. The chirality-assisted aggregation process was utilized to ensure scaffold bending directionality using enantiomerically pure bicyclic angle bars. To address the challenges associated with shifting of the equilibrium from strong cooperative narcissistic self-sorting of self-complementary angle bars in cyclic aggregates toward integrative self-sorting in molecular tweezers, a rational desymmetrization strategy was applied. The dynamic supramolecular tweezer has been shown to display rich supramolecular chemistry, allowing for stimuli-responsive change in aggregate topology and solvent-responsive supramolecular polymerization.

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Sulfoxide hemithioindigo tweezers – visible light addressable capture and release

Abstract: Hemithioindigo based molecular tweezers with a comprehensively improved property profile are obtained by simple oxidation of the sulfur atom.

Cited by 20 publications

References 73 publications

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Photoswitchable molecular tweezers: isomerization to control substrate binding, and what aboutvice versa?

Fully Supramolecular Chiral Hydrogen-Bonded Molecular Tweezer

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